Compounds for optically active devices

ABSTRACT

The present invention relates to novel compounds, particularly to compounds comprising a photoactive unit, said novel compounds being particularly suitable for ophthalmic devices as well as to ophthalmic devices comprising such compounds.

TECHNICAL FIELD

The present invention relates to novel compounds, particularly tocompounds comprising a photoactive unit, said novel compounds beingparticularly suitable for ophthalmic devices as well as to ophthalmicdevices comprising such compounds.

BACKGROUND AND DESCRIPTION OF THE PRIOR ART

Cataract is a general term of an affection of the eye that leads to aloss of vision and in the extreme to blindness by clouding of thenormally clear lens of the eye.

It is the major cause of blindness in the world with it affecting morethan 100 million people. Due to the fact that its major cause is age, itis expected that with the population's average age continuing toincrease the number of cataracts will continue to increase substantiallyin the future.

Effective treatment of cataract is only possible by surgicalintervention, whereby the natural lens of the eye is removed through anincision in the cornea and replaced with an artificial lens, often alsoreferred to as “intraocular lens”. In preparation of surgery currentstate-of-the-art surgical methods employ methods for eye mapping so asto approximate the refractive power best suited to the respectivepatient.

Even though cataract surgery is one of the most widely used and safestsurgical procedures it is not without specific post-surgery problems. Itfrequently happens that the refractive power of the implantedintraocular lens (IOL) is insufficient for restoring good vision. Suchproblems may, for example, be caused by changes in eye geometry inconsequence of the surgery as well as irregular wound healing andpositioning errors that result in the artificial lens not having theoptimal optical properties. As a result the patient will still requirecorrective vision aids, e.g. glasses, to be able to see correctly. Insome cases the resulting refractive power of the implanted artificiallens is so far removed from the required refractive power that furthersurgery will be required. Particularly for aged persons this is notdesirable because the body's capability for healing are reduced withincreasing age. Furthermore, there is the risk of attractingendophthalmitis, an inflammation of the eye, which can even lead to acomplete loss of vision or worse, loss of the eye.

There is therefore a need in the health sector for optically activedevices, and particularly artificial intraocular lenses, that wouldallow for non-invasive adjustment of refractive power after implantationof the lens, thereby preferably further reducing the need forpost-surgery vision aids.

Some developments in this sense have already been made, as for exampleevidenced by WO 2007/033831 A1.

However, the compounds disclosed therein suffer from being too stiff andtoo brittle so that they can't be rolled or folded and are thus not fitto be implanted by state of the art cataract surgical methods,particularly by state of the art micro-incision cataract surgicalmethods.

Consequently, it is an objective of the present application to providefor novel compounds suitable for ophthalmic devices.

It is also an objective of the present application to provide forcompounds, the optical properties of which may be changed, preferably bynon-invasive techniques.

It is a further objective of the present application to provide fornovel compounds that are more flexible than the currently knowncompounds, preferably in combination with being suitable for ophthalmicdevices.

Further advantages and objectives of the compounds of the presentapplication will be evident to the skilled person from the followingdetailed description as well as from the examples.

SUMMARY OF THE INVENTION

The present inventors have now surprisingly found that the above objectsmay be attained either individually or in any combination by thecompounds and ophthalmic devices of the present application.

The present application therefore provides for a compound of formula (I)

wherein

-   -   a is 0 or 1;    -   a′ is 0 or 1;    -   R¹, R² and R³ are at each occurrence independently selected from        the group consisting of H, F, Cl, Br, I, alkyl having from 1 to        20 carbon atoms, partially or completely halogenated alkyl        having from 1 to 20 carbon atoms, aryl and heteroaryl;    -   one of R⁴ and R⁵ is a group of formula (II)

-   -   and the other of R⁴ and R⁵ is selected from the group consisting        of H, F, Cl, Br, I, alkyl having from 1 to 20 carbon atoms,        partially or completely halogenated alkyl having from 1 to 20        carbon atoms, aryl, heteroaryl, and R⁶-Sp-[X¹]_(a)-*;    -   R⁶ is a carbyl group for a′=1 and for a′=0 is selected from the        group consisting of H, F, Cl, Br, I, alkyl having from 1 to 20        carbon atoms, partially or completely halogenated alkyl having        from 1 to 20 carbon atoms, aryl and heteroaryl;    -   Sp is selected from the group consisting of alkanediyl,        alkenediyl and alkyndiyl;    -   X¹, X² and X³ are independently of each other selected from the        group consisting of O, S and N—R¹⁷;    -   R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are at each occurrence independently        of each other selected from the group consisting of H, F, Cl,        Br, I, R⁶-Sp-[X¹]_(a)-*, alkyl having from 1 to 20 carbon atoms,        partially or completely halogenated alkyl having from 1 to 20        carbon atoms, aryl and heteroaryl, provided that at least one of        R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ is R¹⁵;    -   R¹⁵ is at each occurrence independently selected from the group        consisting of alkyl having from 1 to 20 carbon atoms and        partially or completely halogenated alkyl having from 1 to 20        carbon atoms; and    -   R¹⁷ is at each occurrence independently selected from the group        consisting of H, F, Cl, Br, I, alkyl having from 1 to 20 carbon        atoms, partially or completely halogenated alkyl having from 1        to 20 carbon atoms, aryl and heteroaryl,        provided that the compound of formula (I) comprises at least one        group R⁶-Sp-[X¹]_(a)-*.

The present application also provides for a composition comprising saidcompound as well as for an article comprising said composition.

In addition, the present application provides for a process of formingsuch article, said process comprising the steps of

-   -   a) providing a composition comprising said compound;    -   b) subsequently forming the article of said composition.

Furthermore, the present application provides for a process for changingthe optical properties of such article, said process comprising thesteps of

-   -   a) providing said article, and    -   b) subsequently exposing said article to irradiation having a        wavelength of at least 200 nm and at most 1500 nm.

DETAILED DESCRIPTION OF THE INVENTION

For the purposes of the present application an asterisk (“*”) denotes alinkage to an adjacent unit or group or, in case of a polymer, to anadjacent repeating unit or any other group.

For the purposes of the present application the term “organyl group” isused to denote any organic substituent group, regardless of functionaltype, having one free valence at a carbon atom.

For the purposes of the present application the term “organoheterylgroup” is used to denote any univalent group comprising carbon, saidgroup thus being organic, but having the free valence at an atom otherthan carbon.

For the purposes of the present application the term “carbyl group”includes both, organyl groups and organoheteryl groups.

As used herein, the term “carbyl group” will be understood to includeany monovalent or multivalent organic radical moiety which comprises atleast one carbon atom either without any non-carbon atoms (like forexample —C≡C—), or optionally comprising one or more heteroatoms (forexample carbonyl etc.).

The term “hydrocarbyl group” will be understood to mean a carbyl groupthat does additionally contain one or more H atoms and optionallycontains one or more hetero atoms.

As used herein, the term “hetero atom” will be understood to mean anatom in an organic compound that is not a H- or C-atom, and preferablywill be understood to mean N, O, S, P, Si, Se, As, Te or Ge, morepreferably N, O, S, P and Si.

The compound of the present application is of the following formula (I)

wherein a, a′, R¹, R², R³, R⁴, R⁵, R⁶, Sp, X¹, X², X³ and X⁴ are asdefined herein, provided that the compound of formula (I) comprises onegroup R⁶-Sp-[X¹]_(a)-* as defined herein. The expression “comprises onegroup R⁶-Sp-[X¹]_(a)-*” is to denote in this context that the compoundof formula (I) comprises only one such group.

The compound of formula (I) is preferably a compound of formula (I′) ora compound of formula (I″).

a is 0 or 1. Preferably a is 1.

a′ if present is 0 or 1.

R¹, R² and R³ are at each occurrence independently selected from thegroup consisting of H, F, Cl, Br, I, alkyl having from 1 to 20 carbonatoms, partially or completely halogenated alkyl having from 1 to 20carbon atoms, aryl and heteroaryl. Most preferably, R¹, R² and R³ areall H.

One or both, preferably one of R⁴ and R⁵ is a group of formula (II)

with R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ as defined herein. If only one of R⁴ andR⁵ is a group of formula (II), the other of R⁴ and R⁵ is selected fromthe group consisting of H, F, Cl, Br, I, alkyl having from 1 to 20carbon atoms, partially or completely halogenated alkyl having from 1 to20 carbon atoms, aryl, heteroaryl, and R⁶-Sp-[X¹]_(a)-*. Preferably R⁴is H and R⁵ is a group of formula (II) as defined herein.

R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are at each occurrence independently of eachother selected from the group consisting of H, F, Cl, Br, I,R⁶-Sp-[X¹]_(a)-*, alkyl having from 1 to 20 carbon atoms, partially orcompletely halogenated (preferably fluorinated) alkyl having from 1 to20 carbon atoms, aryl and heteroaryl, provided that at least one (forexample, two, three, four or all) of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴,preferably at least one (for example, two or all) of R¹⁰, R¹² and R¹⁴,more preferably at least one or all of R¹⁰ and R¹⁴, and most preferablyR¹⁰ only is R¹⁵ as defined herein.

Preferably, those of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ that are not R¹⁵ are H.

Preferably for the compound of formula (I′) one or both, preferably one,of R⁴ and R⁵ is a group of formula (II) with R¹⁰, R¹¹, R¹², R¹³ and R¹⁴being at each occurrence independently of each other selected from thegroup consisting of H, F, Cl, Br, I, and R¹⁵ as defined herein andpreferably with R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ being at each occurrenceindependently of each other selected from the group consisting of H, F,and R¹⁵ as defined herein, wherein any two adjacent groups of R¹⁰, R¹¹,R¹², R¹³ and R¹⁴ that are R¹⁵ may also form a ring system; and if onlyone of R⁴ and R⁵ is a group of formula (II), the other of R⁴ and R⁵ isselected from the group consisting of H, F, Cl, Br, I, alkyl having from1 to 20 carbon atoms, partially or completely halogenated alkyl havingfrom 1 to 20 carbon atoms, aryl and heteroaryl.

For the compound of formula (I″) one of groups R¹⁰, R¹¹, R¹², R¹³ andR¹⁴ is R⁶-Sp-[X¹]_(a)-*. Thus, preferably for such compound one or both,preferably one, of R⁴ and R⁵ is a group of formula (II) with one of R¹⁰,R¹¹, R¹², R¹³ and R¹⁴ being R⁶-Sp-[X¹]_(a)-* and the others being ateach occurrence independently of each other selected from the groupconsisting of H, F, Cl, Br, I, and R¹⁵ as defined herein, wherein anytwo adjacent groups of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ that are R¹⁵ may alsoform a ring system.

Alternatively, for the compound of formula (I″) one group R⁴ and R⁵ isR⁶-Sp-[X¹]_(a)-*. Thus, preferably for such compound one of R⁴ and R⁵ isR⁶-Sp-[X¹]_(a)-* and the other of R⁴ and R⁵ is a group of formula (II)with R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ being at each occurrence independentlyof each other selected from the group consisting of H, F, Cl, Br, I, andR¹⁵ as defined herein and preferably with R¹⁰, R¹¹, R¹², R¹³ and R¹⁴being at each occurrence independently of each other selected from thegroup consisting of H, F, and R¹⁵ as defined herein, wherein any twoadjacent groups of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ that are R¹⁵ may also forma ring system.

R¹⁵ is at each occurrence independently selected from the groupconsisting of alkyl having from 1 to 20 carbon atoms, partially orcompletely halogenated (preferably fluorinated) alkyl having from 1 to20 carbon atoms, alkoxy having from 1 to 20 carbon atoms, partially orcompletely halogenated alkoxy having from 1 to 20 carbon atoms,thioalkyl having from 1 to 20 carbon atoms, and partially or completelyhalogenated thioalkyl having from 1 to 20 carbon atoms. More preferably,R¹⁵ is at each occurrence independently selected from the groupconsisting of partially or completely halogenated (preferablyfluorinated) alkyl having from 1 to 20 (for example, from 1 to 10 orfrom 1 to 5, or from 1 to 3, or 1) carbon atoms. Most preferably, R¹⁵ is—CF₃.

Any two adjacent groups of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ that are R¹⁵ mayalso form a ring system, preferably a six-membered ring system. Suchring system may be aromatic or non-aromatic. Such ring system, ifnon-aromatic, may be saturated or unsaturated, for example comprising adouble bond. Optionally such ring system may be substituted, i.e. one ormore of the hydrogens is replaced with H, F, Cl, Br, I, alkyl havingfrom 1 to 20 carbon atoms, partially or completely halogenated alkylhaving from 1 to 20 carbon atoms, aryl and heteroaryl.

R⁶ is a carbyl group for a′=1 and for a′=0 is selected from the groupconsisting of H, F, Cl, Br, I, alkyl having from 1 to 20 carbon atoms,partially or completely halogenated alkyl having from 1 to 20 carbonatoms, aryl and heteroaryl.

A carbyl or hydrocarbyl group comprising a chain of 3 or more C atomsmay be straight-chain, branched and/or cyclic, including spiro and/orfused rings.

Preferred carbyl and hydrocarbyl groups include alkyl, alkoxy,alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy,each of which is optionally substituted and has 1 to 40, preferably 1 to25, very preferably 1 to 18 C atoms, furthermore optionally substitutedaryl or aryloxy having 6 to 40, preferably 6 to 25 C atoms, furthermorealkylaryloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy andaryloxycarbonyloxy, each of which is optionally substituted and has 6 to40, preferably 7 to 30 C atoms, wherein all these groups do optionallycontain one or more hetero atoms, preferably selected from N, O, S, P,Si, Se, As, Te and Ge, more preferably N, O, S, P and Si.

The carbyl or hydrocarbyl group may be a saturated or unsaturatedacyclic group, or a saturated or unsaturated cyclic group. Unsaturatedacyclic or cyclic groups are preferred, especially aryl, alkenyl andalkynyl groups. Where the C₁-C₄₀ carbyl or hydrocarbyl group is acyclic,the group may be straight-chain or branched. The C₁-C₄₀ carbyl orhydrocarbyl group includes for example: a C₁-C₄₀ alkyl group, a C₁-C₄₀fluoroalkyl group, a C₁-C₄₀ alkoxy or oxaalkyl group, a C₂-C₄₀ alkenylgroup, a C₂-C₄₀ alkynyl group, a C₃-C₄₀ allyl group, a C₄-C₄₀alkyldienyl group, a C₄-C₄₀ polyenyl group, a C₂-C₄₀ ketone group, aC₂-C₄₀ ester group, a C₆-C₁₈ aryl group, a C₆-C₄₀ alkylaryl group, aC₆-C₄₀ arylalkyl group, a C₄-C₄₀ cycloalkyl group, a C₄-C₄₀ cycloalkenylgroup, and the like. Preferred among the foregoing groups are a C₁-C₂₀alkyl group, a C₁-C₂₀ fluoroalkyl group, a C₂-C₂₀ alkenyl group, aC₂-C₂₀ alkynyl group, a C₃-C₂₀ allyl group, a C₄-C₂₀ alkyldienyl group,a C₂-C₂₀ ketone group, a C₂-C₂₀ ester group, a C₆-C₁₂ aryl group, and aC₄-C₂₀ polyenyl group, respectively.

The terms “aryl” and “heteroaryl” as used herein preferably mean amono-, bi- or tricyclic aromatic or heteroaromatic group with 4 to 30ring C atoms that may also comprise condensed rings and is optionallysubstituted with one or more groups L, wherein L is selected fromhalogen, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)NR⁰R⁰⁰, —C(═O)X⁰,—C(═O)R⁰, —NH₂, —NR⁰R⁰⁰, —SH, —SR⁰, —SO₃H, —SO₂R⁰, —OH, —NO₂, —CF₃,—SF₅, or carbyl or hydrocarbyl with 1 to 40 C atoms that is optionallysubstituted and optionally comprises one or more hetero atoms, and ispreferably alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl oralkoxycarbonyloxy with 1 to 20 C atoms that is optionally fluorinated,and R⁰, R⁰⁰ and X⁰ have the meanings given above and below.

R⁰, R⁰⁰ and R⁰⁰⁰ are at each occurrence independently of each otherselected from the group consisting of H, F and hydrocarbyl having from 1to 40 carbon atoms. Said hydrocarbyl preferably has at least 5 carbonatoms. Said hydrocarbyl preferably has at most 30, more preferably atmost 25 or 20, even more preferably at most 20, and most preferably atmost 12 carbon atoms. Preferably, R⁰, R⁰⁰ and R⁰⁰⁰ are at eachoccurrence independently of each other selected from the groupconsisting of H, F, alkyl, fluorinated alkyl, alkenyl, alkynyl, phenyland fluorinated phenyl. More preferably, R⁰, R⁰⁰ and R⁰⁰⁰ are at eachoccurrence independently of each other selected from the groupconsisting of H, F, alkyl, fluorinated, preferably perfluorinated,alkyl, phenyl and fluorinated, preferably perfluorinated, phenyl.

It is noted that for example alkyl suitable as R⁰, R⁰⁰ and R⁰⁰⁰ alsoincludes perfluorinated alkyl, i.e. alkyl wherein all of the hydrogenare replaced by fluorine. Examples of suitable alkyls may be selectedfrom the group consisting of methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, tert-butyl (or “t-butyl”), pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (—C₂₀H₄₁).

X⁰ is halogen. Preferably X⁰ is selected from the group consisting of F,Cl and Br.

Very preferred substituents L are selected from halogen, most preferablyF, or alkyl, alkoxy, oxoalkyl, thioalkyl, fluoroalkyl and fluoroalkoxywith 1 to 12 C atoms or alkenyl and alkynyl with 2 to 12 C atoms.

Especially preferred aryl and heteroaryl groups are phenyl, phenylwherein one or more CH groups are replaced by N, naphthalene, thiophene,selenophene, thienothiophene, dithienothiophene, fluorene and oxazole,all of which can be unsubstituted, mono- or polysubstituted with L asdefined above. Very preferred rings are selected from pyrrole,preferably N-pyrrole, furan, pyridine, preferably 2- or 3-pyridine,pyrimidine, pyridazine, pyrazine, triazole, tetrazole, pyrazole,imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole,oxadiazole, thiophene, preferably 2-thiophene, selenophene, preferably2-selenophene, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene,furo[3,2-b]furan, furo[2,3-b]furan, seleno[3,2-b]selenophene,seleno[2,3-b]selenophene, thieno[3,2-b]selenophene, thieno[3,2-b]furan,indole, isoindole, benzo[b]furan, benzo[b]thiophene,benzo[1,2-b;4,5-b′]dithiophene, benzo[2,1-b;3,4-b′]dithiophene, quinole,2-methylquinole, isoquinole, quinoxaline, quinazoline, benzotriazole,benzimidazole, benzothiazole, benzisothiazole, benzisoxazole,benzoxadiazole, benzoxazole, benzothiadiazole, all of which can beunsubstituted, mono- or polysubstituted with L as defined above.

An alkyl or alkoxy radical, i.e. where the terminal CH₂ group isreplaced by —O—, can be straight-chain or branched. It is preferablystraight-chain (or linear). Suitable examples of such alkyl and alkoxyradical are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl,tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, ethoxy, propoxy,butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, ethylhexyl,undecoxy, dodecoxy, tridecoxy or tetradecoxy. Preferred alkyl and alkoxyradicals have 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Suitableexamples of such preferred alkyl and alkoxy radicals may be selectedfrom the group consisting of methyl, ethyl, n-propyl, iso-propyl,n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethylhexyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy,heptoxy, octoxy, nonoxy and decoxy.

An alkenyl group, wherein one or more CH₂ groups are replaced by —CH═CH—can be straight-chain or branched. It is preferably straight-chain, has2 to 10 C atoms and accordingly is preferably vinyl, prop-1-enyl,prop-2-enyl, but-1-enyl, but-2-enyl, but-3-enyl, pent-1-enyl,pent-2-enyl, pent-3-enyl or pent-4-enyl, hex-1-enyl, hex-2-enyl,hex-3-enyl, hex-4-enyl or hex-5-enyl, hept-1-enyl, hept-2-enyl,hept-3-enyl, hept-4-enyl, hept-5-enyl or hept-6-enyl, oct-1-enyl,oct-2-enyl, oct-3-enyl, oct-4-enyl, oct-5-enyl, oct-6-enyl oroct-7-enyl, non-1-enyl, non-2-enyl, non-3-enyl, non-4-enyl, non-5-enyl,non-6-enyl, non-7-enyl or non-8-enyl, dec-1-enyl, dec-2-enyl,dec-3-enyl, dec-4-enyl, dec-5-enyl, dec-6-enyl, dec-7-enyl, dec-8-enylor dec-9-enyl.

Especially preferred alkenyl groups are C₂-C₇-1E-alkenyl,C₄-C₇-3E-alkenyl, C₅-C₇-4-alkenyl, C₆-C₇-5-alkenyl and C₇-6-alkenyl, inparticular C₂-C₇-1E-alkenyl, C₄-C₂-3E-alkenyl and C₅-C₇-4-alkenyl.Examples for particularly preferred alkenyl groups are vinyl,1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl,3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl,4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Alkenylgroups having up to 5 C atoms are generally preferred.

An oxoalkyl group, i.e. where one CH₂ group is replaced by —O—, ispreferably straight-chain 2-oxapropyl (=methoxymethyl),2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3-, or4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or 6-oxaheptyl,2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonylor 2-, 3-, 4-, 5-, 6-,7-, 8- or 9-oxadecyl, for example, oxaalkyl, i.e.where one CH₂ group is replaced by —O—, is preferably straight-chain2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl(=2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl,2-, 3-, 4-, 5-, or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-,3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-,7-, 8- or9-oxadecyl, for example.

In an alkyl group wherein one CH₂ group is replaced by —O— and one by—C(O)—, these radicals are preferably neighboured. Accordingly theseradicals together form a carbonyloxy group —C(O)—O— or an oxycarbonylgroup —O—C(O)—. Preferably this group is straight-chain and has 2 to 6 Catoms. It is accordingly preferably selected from the group consistingof acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy,acetyloxymethyl, propionyloxymethyl, butyryloxymethyl,pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl,2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl,4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,butoxycarbonyl, pentoxycarbonyl, methoxycarbonyl methyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonyl methyl,2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl,2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl,3-(ethoxycarbonyl)propyl, and 4-(methoxycarbonyl)-butyl.

An alkyl group wherein two or more CH₂ groups are replaced by —O— and/or—C(O)O— can be straight-chain or branched. It is preferablystraight-chain and has 3 to 12 C atoms. Accordingly it is preferablyselected from the group consisting of bis-carboxy-methyl,2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl,5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl,8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl,bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl,3,3-bis-(methoxycarbonyl)-propyl, 4,4-bis-(methoxycarbonyl)-butyl,5,5-bis-(methoxycarbonyl)-pentyl, 6,6-bis-(methoxycarbonyl)-hexyl,7,7-bis-(methoxycarbonyl)-heptyl, 8,8-bis-(methoxycarbonyl)-octyl,bis-(ethoxycarbonyl)-methyl, 2,2-bis-(ethoxycarbonyl)-ethyl,3,3-bis-(ethoxycarbonyl)-propyl, 4,4-bis-(ethoxycarbonyl)-butyl, and5,5-bis-(ethoxycarbonyl)-hexyl.

A thioalkyl group, i.e. where one CH₂ group is replaced by —S—, ispreferably straight-chain thiomethyl (—SCH₃), 1-thioethyl (—SCH₂CH₃),1-thiopropyl (═—SCH₂CH₂CH₃), 1-(thiobutyl), 1-(thiopentyl),1-(thiohexyl), 1-(thioheptyl), 1-(thiooctyl), 1-(thiononyl),1-(thiodecyl), 1-(thioundecyl) or 1-(thiododecyl), wherein preferablythe CH₂ group adjacent to the sp² hybridised vinyl carbon atom isreplaced.

A fluoroalkyl group is preferably perfluoroalkyl C_(i)F₂₊₁, wherein i isan integer from 1 to 15, in particular CF₃, C₂F₅, C₃F₇, C₄F₉, C₅F₁₁,C₆F₁₃, C₇F₁₅ or C₈F₁₇, very preferably C₆F₁₃, or partially fluorinatedalkyl, in particular 1,1-difluoroalkyl, all of which are straight-chainor branched.

Alkyl, alkoxy, alkenyl, oxaalkyl, thioalkyl, carbonyl and carbonyloxygroups can be achiral or chiral groups. Particularly preferred chiralgroups are 2-butyl (=1-methylpropyl), 2-methylbutyl, 2-methylpentyl,3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, in particular2-methylbutyl, 2-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy,2-ethyl-hexoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa-3-methylbutyl,3-oxa-4-methyl-pentyl, 4-methylhexyl, 2-hexyl, 2-octyl, 2-nonyl,2-decyl, 2-dodecyl, 6-meth-oxyoctoxy, 6-methyloctoxy,6-methyloctanoyloxy, 5-methylheptyloxy-carbonyl, 2-methylbutyryloxy,3-methylvaleroyloxy, 4-methylhexanoyloxy, 2-chloropropionyloxy,2-chloro-3-methylbutyryloxy, 2-chloro-4-methyl-valeryl-oxy,2-chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxa-hexyl,1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy,1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy,1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2-octyl,2-fluoromethyloctyloxy for example. Very preferred are 2-hexyl, 2-octyl,2-octyloxy, 1,1,1-trifluoro-2-hexyl, 1,1,1-trifluoro-2-octyl and1,1,1-trifluoro-2-octyloxy.

Preferred achiral branched groups are isopropyl, isobutyl(=methylpropyl), isopentyl (=3-methylbutyl), sec-butyl, tert-butyl,isopropoxy, 2-methyl-propoxy, 3-methylbutoxy, duryl and ethylhexyl.

In a preferred embodiment, the hydrocarbyl groups are independently ofeach other selected from primary, secondary or tertiary alkyl or alkoxywith 1 to 30 C atoms, wherein one or more H atoms are optionallyreplaced by F, or aryl, aryloxy, heteroaryl or heteroaryloxy that isoptionally alkylated or alkoxylated and has 4 to 30 ring atoms. Verypreferred groups of this type are selected from the group consisting ofthe following formulae

wherein “ALK” denotes optionally fluorinated alkyl or alkoxy with 1 to20, preferably 1 to 12 C-atoms, in case of tertiary groups verypreferably 1 to 9 C atoms.

Sp is selected from the group consisting of alkanediyl, alkenediyl andalkyndiyl (*—C≡C—*).

Preferably said alkanediyl has at least 1 carbon atom, more preferablyat least 2 or 3 carbon atoms, even more preferably at least 4 carbonatoms, still even more preferably at least 5 carbon atoms, and mostpreferably at least 6 carbon atoms. Preferably said alkenediyl has atleast 2 carbon atoms, more preferably at least 3 carbon atoms, even morepreferably at least 4 carbon atoms, still even more preferably at least5 carbon atoms, and most preferably at least 6 carbon atoms.

Preferably said alkyndiyl has at least 3 carbon atoms, more preferablyat least 4 carbon atoms, even more preferably at least 5 carbon atoms,and most preferably at least 6 carbon atoms.

Preferably said alkanediyl, alkenediyl or alkyndiyl has at most 20carbon atoms, more preferably at most 19 or 18 carbon atoms, even morepreferably at most 17 or 16 carbon atoms, still even more preferably atmost 15 or 14 carbon atoms and most preferably at most 13 or 12 carbonatoms.

Preferably, Sp selected from the group consisting of alkanediyl,alkenediyl and alkyndiyl (*—C≡C—*), wherein at least one, preferably atleast two hydrogen has/have been replaced with R¹⁶.

R¹⁶ may be selected from the group consisting of OH, alkyl having from 1to 10 (preferably from 1 to 5) carbon atoms, partially or completelyhalogenated (preferably fluorinated) alkyl having from 1 to 10(preferably from 1 to 5) carbon atoms, alkoxy having from 1 to 10(preferably from 1 to 5) carbon atoms, and partially or completelyhalogenated (preferably fluorinated) alkoxy having from 1 to 10(preferably from 1 to 5) carbon atoms. Preferably R¹⁶ is OH.

Sp may, for example, be represented by the following formula (III)—[C(R⁷)(R⁸)]_(b)—  (III)wherein b, R⁷ and R⁸ are as defined herein.

b is at least 1, preferably at least 2, more preferably at least 4, evenmore preferably at least 5. b is at most 20, preferably at most 19, morepreferably at most 18, even more preferably at most 17, still even morepreferably at most 16 and most preferably at most 15.

If b is at least two, two neighboring groups C(R⁷)(R⁸) may be replacedby an alkenediyl.

If b is at least three, two neighboring groups C(R⁷)(R⁸) may be replacedby an alkyndiyl.

R⁷ and R⁸ are independently of each other H or R¹⁶. Preferably at leastone of the R⁷ and R⁸ present is R¹⁶. More preferably at least two of theR⁷ and R⁸ present are R¹⁶.

Alternatively Sp may, for example, be represented by the followingformulae (III-a)—[C(R^(7′))(R^(8′))]_(b1)—[C(R^(7″))(R^(8′))]_(b2)—[C(R^(7′″))(R^(8′″))]_(b3)—  (III-a)wherein R^(7′), R^(8′), R^(7″), R^(8″), R^(7′″), R^(8′″), b1, b2 and b3are as defined herein.

The sum of b1, b2 and b3 is b, i.e. b1+b2+b3=b. Preferably, at least oneof b1 or b3 is at least 1 and b2 is 1. More preferably b1, b2 and b3 areall at least 1. Most preferably b1 and b3 are at least 1 and b2 is 1.

If b1 is at least two, two neighboring groups C(R^(7′))(R^(8′)) may bereplaced by an alkenediyl. If b2 is at least two, two neighboring groupsC(R^(7″))(R^(8″)) may be replaced by an alkenediyl. If b3 is at leasttwo, two neighboring groups C(R^(7′″))(R^(8′″)) may be replaced by analkenediyl.

If b1 is at least two, two neighboring groups C(R^(7′))(R^(8′)) may bereplaced by an alkyndiyl. If b2 is at least two, two neighboring groupsC(R^(7″))(R^(8″)) may be replaced by an alkyndiyl. If b3 is at leasttwo, two neighboring groups C(R^(7′″))(R^(8′″)) may be replaced by analkyndiyl.

Preferably R^(7′), R^(8′), R^(7′″) and R^(8′″)—if present—are H and atleast one of R^(7″) and R^(8″) is R¹⁶.

Suitable examples of Sp may be selected from the following formulae(III-1) to (III-10)

X¹, X² and X³ are independently of each other selected from the groupconsisting of O, S and N—R¹⁷ with R¹⁷ as defined herein.

Preferably X¹ is O.

Preferably X² is O or S. Most preferably X² is O.

Preferably X³ is O or N—R¹⁷. Most preferably X³ is N—R¹⁷.

R¹⁷ is at each occurrence independently selected from the groupconsisting of H, alkyl having from 1 to 20 carbon atoms, partially orcompletely halogenated alkyl having from 1 to 20 carbon atoms and aryl.Preferably R¹⁷ is H.

Preferably, the compound of formula (I) is an olefinic compound, whereinR⁶ comprises an olefinically unsaturated group. Preferably R⁶ is a groupof formula (IV-A)

wherein X⁴, c, R²⁰, R²¹ and R²² are as defined herein.

More preferably said olefinic compound comprises a group of formula(IV-A′)

wherein X¹, a, Sp, X⁴, c, R²⁰, R²¹ and R²² are as defined herein.

Preferred examples of such olefinic compounds may be represented by anyone selected from the group consisting of formulae (I-A′), (I-A″-1),(I-A″-2), (I-A″'-1) and (I-A′″-2)

wherein one of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ is a group of formulaR⁶-Sp-[X¹]_(a)-* and R⁶ is a group of formula (IV-A) as defined herein;

wherein one of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ is a group of formulaR⁶-Sp-[X¹]_(a)-* and R⁶ is a group of formula (IV-A) as defined herein;

wherein R¹, R², R³, R⁴, R⁵, X¹, X², X³, X⁴, a, c, R²⁰, R²¹ and R²² areas defined herein.

c is 0 or 1.

R²⁰, R²¹ and R²² are carbyl. Preferably R²⁰, R²¹ and R²² are at eachoccurrence independently of each other selected from the groupconsisting of H, F, alkyl having from 1 to 20 carbon atoms, partially orcompletely halogenated alkyl having from 1 to 20 carbon atoms, aryl andheteroaryl. More preferably R²⁰, R²¹ and R²² are at each occurrenceindependently of each other selected from the group consisting of H, F,alkyl having from 1 to 20 carbon atoms, partially or completelyhalogenated alkyl having from 1 to 20 carbon atoms and aryl.

X⁴ is selected from the group consisting of O, S, C(═O), C(═O)O andN—R¹⁷, with R¹⁷ as defined herein. Preferably X⁴ is O.

It is noted that C(═O)O may be inserted in any direction, i.e. C(═O)Owith the —O— group adjacent to Sp or OC(═O) with the —O— group adjacentto the olefinically unsaturated group.

The synthesis of the present compounds can be done using reactions thatare well known to the skilled person. An exemplary synthesis of thenovel core structure within this invention is shown in the Scheme 1.Beginning with (E)-cinnamic acid, the acid was converted to thecorresponding cinnamoyl chloride under standard conditions. Then, theacid chloride compound was treated with the aniline derivative to obtainthe amide compound. The final step was an iodine mediated ring-closurereaction, which contains a rearrangement step. This reaction is known tothe chemical expert and prior art from the literature (Org. Lett. 2013,15, 2906-2909, see also DOI: 10.1021/o1400743r).

The core structure can be subtle modified through the incorporation offunctional groups for further derivatization. On the one hand side, theaniline-derivate could be equipped with a para-hydroxy group. As thesecond opportunity, the cinnamic acid derivative could be alsofunctionalized with a para-hydroxy group.

To then obtain the final monomer, the lactame derivative was alkylatedwith an aliphatic bromo-alcohol-derivative. This compound was thenfinally treated with the corresponding acrylate-derivative. Exemplaryreaction sequences are shown in Scheme 2a and Scheme 2b.

Preferably the compound of the present application is an oligomer orpolymer, wherein R⁶ is the polymer backbone or wherein R⁶ is part of thepolymer backbone. Preferably, such oligomer or polymer comprises aconstitutional unit M⁰ of formula (IV-B), i.e. R⁶ is a group of formula(IV-B)

wherein X⁴, c, R²⁰, R²¹ and R²² are as defined herein. More preferably,such oligomer or polymer comprises a constitutional unit M⁰ of formula(IV-B′)

Preferably, such oligomer or polymer comprises at least oneconstitutional unit M¹ selected from the group consisting of thefollowing formulae (I-B′), (I-B″-1), (I-B″-2), (I-B″-1) and (I-B′″-2)

wherein one of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ is a group of formulaR⁶-Sp-[X¹]_(a)-* and R⁶ is a group of formula (IV-B) as defined herein;

wherein one of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ is a group of formulaR⁶-Sp-[X¹]_(a)-* and R⁶ is a group of formula (IV-B) as defined herein;

said at least one unit M¹ being if there are two or more, at eachoccurrence the same or different, wherein R¹, R², R³, R⁴, R⁵, X¹, X²,X³, X⁴, a, c, R²⁰, R²¹ and R²² are as defined herein.

The compound of formula (I) may be a copolymer, i.e. an oligomer orpolymer comprising one or more constitutional unit M¹ of formula (I-B),which may be the same or different from one another, and one or moreconstitutional units M², which may the same or different from oneanother. Said one or more constitutional units M² are chemicallydifferent from the units M¹. Preferably, said one or more constitutionalunits M² are derived by polymerization of one or more monomers selectedfrom the group consisting of ethylene, propylene, acrylate, methacrylateand styrene.

Preferably the compound of formula (I) may be a homopolymer, i.e. anoligomer or polymer comprising one or more constitutional unit M¹ offormula (I-B), wherein all constitutional units M¹ are the same.

Exemplary compounds of formula (I) may be selected from the followingformulae (M-1) to (M-47)

Exemplary oligomeric and polymeric compounds of formula (I) may beselected from the following formulae (P-1) to (P-47)

For the purposes of the present application the term “derived bypolymerization” is used to indicate that a double bond is formallyturned into a single bond and two linkages to other atoms, said linkagesbeing indicated by the two asterisks:

Preferably said copolymer comprises the one or more constitutional unitsM¹ in a molar ratio m₁ and the one or more constitutional units M² in amolar ratio m₂, wherein the ratio m₁:m₂ is at least 0.01 and at most100.

The present oligomers and polymers may be made by any suitable method.It is, however, preferred that the present oligomers and polymers aremade by radical polymerization, wherein the polymerization reaction isstarted by means of a suitable radical polymerization initiator. For thepurposes of the present application the type of radical polymerizationinitiator is not particularly limited and may be any suitable radicalgenerating compound. Such compounds are well known to the skilledperson. Suitable polymerization initiators may be selected from thermalinitiators or photoinitiators, i.e. compounds that generate radicals byexposure to heat or irradiation with light of a suitable wavelength.Examples of suitable thermal polymerization initiators may be selectedfrom the groups of compounds comprising one or more peroxide groups,i.e. compounds comprising a group —O—O—, and/or compounds comprising oneor more azo groups, i.e. compounds comprising a group —N≡N—.

Suitable polymerization initiators comprising one or more peroxidegroups may, for example, be selected from the groups consisting oft-butyl(peroxy-2-ethyl-hexanoate),di-(tert-butylcyclohexyl)peroxydicarbonate and benzoylperoxide.

Suitable polymerization initiators comprising one or more azo groupsmay, for example, be selected from the group consisting of1,1′-azobis(cyclohexancarbonitrile) and2,2′azobis(cyclohexanecarbonitrile) (AIBN).

A suitable example of a photoinitiator isdimethylaminobenzoate/champherchinone

If a photoinitiator is used as polymerization initiator, it is preferredthat the wavelength required to decompose said photoinitiator isdifferent from the wavelength needed to irradiate the compound of thepresent application so as to change its optical properties.

Preferably, the radical initiators are used in an amount of at least0.0001 eq and of at most 0.1 eq of the main monomer. Such radicalinitiators could be thermal initiators, e.g. azobisisobutyronitrile(AIBN) or photochemical initiators likedimethylaminobenzoate/champherchinone.

The present application also provides for a composition comprising thecompound of formula (I). Depending upon the intended use suchcomposition may comprise further different components. Such furthercomponents may, for example, be selected from the group consisting of UVabsorbers, antioxidants and crosslinkers.

The UV absorber that may be used in the present composition is notparticularly limited and can easily be selected from those generallyknown to the skilled person. Generally suitable UV absorbers arecharacterized by being unsaturated compounds, preferably compoundscomprising one or more selected from group consisting of olefinicgroups, aryl groups and heteroaryl groups; these groups may be presentin any combination.

Suitable UV-absorbers for use in the present composition may, forexample, be selected from those comprising a group selected frombenzotriazole, benzophenone and triazine. Suitable UV-absorbers are, forexample, disclosed in U.S. Pat. Nos. 5,290,892; 5,331,073 and 5,693,095.

Suitable crosslinkers may be used to impart elastomeric properties tothe present composition and the articles produced therewith. Typicallyany suitable di- or tri-functional monomer may be used as crosslinker.Such monomers are generally well known to the skilled person.

The present compound of formula (I) is particularly well suited for usein optically active devices. Hence the present application also providesfor optically active devices comprising the compound of formula (I).Preferred optically active devices are ophthalmic devices. Examples ofsuch ophthalmic devices include lenses, keratoprostheses, and corneainlays or rings. More preferably, said optically active device is alens. Most preferably, such optically active device is an intraocularlens, which may, for example, be a posterior chamber intraocular lens oran anterior chamber intraocular lens.

The present optically active devices may be formed by a processcomprising the steps of

-   -   a) providing a composition comprising the compound as defined        herein; and    -   b) subsequently forming the article of said composition.

Intraocular lenses in accordance with the present application arebelieved to show particularly advantageous properties in that they areflexible enough so as to be rolled or folded and consequently requiringa much smaller incision for them to be inserted into the eye. It isbelieved that this will allow for improved healing of the eye,particularly in respect to the time for the eye to heal.

The type of intraocular lens is not limited in any way. It may, forexample, comprise one or more optic and one or more haptic components,wherein the one or more optic components serve as lens and the one ormore haptic components are attached to the one or more optic componentsand hold the one or more optic components in place in the eye. Thepresent intraocular lens may be of a one-piece design or of multi-piecedesign, depending on whether the one or more optic components and theone or more haptic components are formed from a single piece of material(one-piece design) or are made separately and then combined (multi-piecedesign). The present intraocular lens is also designed in such a waythat it allows to be, for example, rolled up or folded small enough sothat it fits through an incision in the eye, said incision being assmall as possible, for example, at most 3 mm in length.

Additionally, intraocular lenses in accordance with the presentapplication allow for the non-invasive adjustment of the opticalproperties, particularly the refractive power, after implantation of thelens into the eye, thus reducing the need for post-surgery vision aidsor reducing or totally avoiding follow-up surgery.

In order to change the optical properties and particularly therefractive power of the intraocular lens it is exposed to irradiationhaving a wavelength of at least 200 nm and of at most 1500 nm. Hence,the present application also provides for a process of changing theoptical properties of an optically active article as defined herein,said process comprising the steps of

-   -   a) providing an article as defined herein; and    -   b) subsequently exposing said article to irradiation having a        wavelength of at least 200 nm and at most 1500 nm.

Preferably, said irradiation has a wavelength of at least 250 nm or 300nm, more preferably of at least 350 nm, even more preferably of at least400 nm, still even more preferably of at least 450 nm, and mostpreferably of at least 500 nm. Preferably, said irradiation has awavelength of at most 1400 nm or 1300 nm or 1200 nm or 1100 nm or 1000nm, more preferably of at most 950 nm or 900 nm, even more preferably ofat most 850 nm, still even more preferably of at most 800 nm and mostpreferably of at most 750 nm.

EXAMPLES

The following examples are intended to show the advantages of thepresent compounds in a non-limiting way.

Unless indicated otherwise, all syntheses were carried out under aninert atmosphere using dried (i.e. water-free) solvents. Solvents andreagents were purchased from Sigma-Aldrich or ABCR.

DCM is used to denote dichloromethane. DMF is used to denotedimethylformamide. EE is used to denote ethyl acetate.

Example 1 Cinnamoyl Chloride Derivative

To a suspension of (E)-3-(4-methoxyphenyl)acrylic acid (1.0 equiv.) inDCM was added a catalytic amount of DMF (0.1 mL/mmol acid). At ambienttemperature, oxalylchloride (1.5 equiv.) was added dropwise, resultingin a homogenous solution. This solution was further stirred at roomtemperature overnight. DCM was removed under reduced pressure and ayellow-brownish emulsion was obtained. A yield was not determined andthe obtained crude product was used without characterization in the nextstep.

Example 2 Amide Derivative

The obtained residue from the previous reaction was dissolved in dryDCM. Then a solution of N-isopropylaniline (1.0 equiv.) and Et₃N (2.5equiv.) in DCM (0.25 M) was slowly added dropwise. The solution wasstirred at room temperature overnight. After completion of the reaction,dist. H₂O was added to the reaction mixture, and the mixture wasextracted with DCM. The organic phase was washed with saturated NH₄Cl,NaCl and dist. H₂O. After evaporation of the solvent, the crude residuewas purified via chromatography using cyclohexane/EE as an eluentyielding the product in approximately 50% as a light brown solid. TheNMR-data matches well with those reported in the literature.

¹H NMR (500 MHz, CDCl₃) δ 7.60 (d, 1H, J=16.2 Hz), 7.46-7.40 (m, 3H),7.20-7.15 (m, 4H), 6.78 (d, 2H, J=8.9 Hz), 5.95 (d, 1H, J=15.6 Hz), 3.79(s, 3H), 3.46 (s, 3H).

Analogously the following aniline-derivatives may be used to synthesizethe compounds indicated as “Product” in the following table:

Aniline-derivative Product Yield [%]

65

70

72

69

76

54

Example 3 Synthesis of 1-isopropyl-3-phenylquinolin-2(1H)-one

The synthesis 1-isopropyl-3-phenylquinolin-2(1H)-one was analogouslyperformed according to the literature procedure (Org. Lett. 2013, 15,2906-2909, see also DOI: 10.1021/o1400743r). The product could beobtained in 60% yield as a yellow solid. The NMR-data is in goodagreement with those reported in the literature Analogously thefollowing amide-derivatives may be used to synthesize the compoundsindicated as “Product” in the following table:

Amide-derivative Product Yield [%]

45

42

48

47

40

39

Selected NMR Data

¹H NMR (500 MHz, CDCl₃) δ 7.80 (s, 1H), 7.72 (d, 2H, J=8.9 Hz), 7.63 (d,1H, J=7.9 Hz), 7.58 (t, 1H, J=8.0 Hz), 7.40 (d, 1H, J=8.6 Hz), 7.28 (d,1H, J=8.0 Hz), 7.01 (d, 2H, J=8.8 Hz), 3.89 (s, 3H), 3.83 (s, 3H)

¹H NMR (500 MHz, CDCl₃) δ 7.96 (s, 1H), 7.85 (d, 1H, J=8.3 Hz), 7.73 (d,1H, J=7.9 Hz), 7.62-7.58 (m, 3H), 7.37 (t, 1H, J=7.5 Hz), 6.99 (d, 2H,J=8.7 Hz), 4.53 (t, 2H, J=6.7 Hz), 3.88 (s, 3H), 1.86-1.80 (m, 2H),1.49-1.37 (m, 4H), 0.94 (t, 3H, J=7.1 Hz)

Example 4 Preparation of the Phenol-Derivatives

To a solution of the 1-alkyl-3-phenylquinolin-2(1H)-one-derivative inDCM was added BBr₃ (2.0 equiv.) at 0° C. The resulting mixture washeated up to reflux overnight. After cooling down the reaction mixtureto room temperature, it was poured on an ice/water mixture, filtratedand the resulting solid was dried in vacuo. The phenol derivative wasobtained in 89% yield.

Analogously, other phenol derivatives were prepared in the same manner:

1-Alkyl-3-phenylquinolin- 2(1H)-one Product Yield [%]

92

89

85

75

64

71

Selected NMR Data

¹H NMR (500 MHz, CDCl₃) δ 7.79 (s, 1H), 7.63 (d, 1H, J=7.6 Hz), 7.59 (t,1H, J=7.6 Hz), 7.55 (d, 2H, J=8.6 Hz), 7.42 (d, 1H, J=8.6 Hz), 7.28 (t,1H, J=7.6 Hz), 6.85 (d, 2H, J=8.6 Hz), 6.23 (s, 1H), 3.85 (s, 3H)

¹H NMR (500 MHz, CDCl₃) δ 7.95 (s, 1H), 7.84 (d, 1H, J=8.4 Hz), 7.73 (d,1H, J=8.0 Hz), 7.59 (td, 1H, J₁=8.4 Hz, J₂=1.4 Hz), 7.55 (d, 2H, J=7.5Hz), 7.37 (t, 1H, J=7.5 Hz), 6.91 (d, 2H, J=8.7 Hz), 4.84 (s, 1H), 4.52(t, 2H, J=6.7 Hz), 1.85-1.79 (m, 2H), 1.48-1.44 (m, 1H), 1.42-1.36 (m,2H), 0.92j (t, 3H, J=7.2 Hz)

Example 5 Introduction of Aliphatic Side Chains

3-(4-hydroxyphenyl)-1-isopropylquinolin-2(1H)-one and12-bromododecan-1-ol (1.05 equiv.) were dissolved in acetone. Then,K₂CO₃ was added and the suspension was heated up to reflux untilcompletion of the reaction. The reaction mixture was filtrated and theseparated solid was thoroughly washed with additional acetone. Thefiltrate was concentrated in vacuo and the crude product was purifiedvia column chromatography using cyclohexane/EE as an eluent.3-(4-(12-hydroxydodecyl)phenyl)-1-isopropylquinolin-2(1H)-one could beisolated in 85% as a pale yellow solid.

Accordingly several other bromo-alcohols were applied in theWilliamson-Ether synthesis as well:

3-(4-Hydroxyphenyl)-1- isopropylquinolin-2(1H)-one Product Yield [%]

87

82

89

Selected NMR Data

¹H NMR (500 MHz, CDCl₃) δ 7.76 (s, 1H), 7.67 (d, 2H, J=8.8 Hz), 7.60 (d,1H, J=7.5 Hz), 7.55 (t, 1H, J=7.9 Hz), 7.37 (d, 1H, J=8.5 Hz), 7.24 (t,1H, J=7.4 Hz), 6.96 (d, 2H, J=8.5 Hz), 4.01 (t, 2H, J=6.5 Hz), 3.80 (s,3H), 3.64 (t, 2H, J=5.7 Hz), 1.83-1.77 (m, 2H), 1.60-1.54 (m, 2H),1.50-1.43 (m, 2H), 1.39-1.24 (m, 16H)

¹H NMR (500 MHz, CDCl₃) δ 7.95 (s, 1H), 7.84 (d, 1H, J=8.3 Hz), 7.73 (d,1H, J=7.9 Hz), 7.60-7.58 (m, 3H), 7.36 (t, 1H, J=7.5 Hz), 6.97 (d, 2H,J=8.7 Hz), 4.52 (t, 2H, J=6.7 Hz), 4.02 (t, 2H, J=6.6 Hz), 3.64 (q, 2H,J=6.5 Hz), 1.85-1.79 (m, 4H), 1.60-1.56 (m, 2H), 1.50-1.45 (m, 3H),1.40-1.30 (m, 16H), 1.19 (t, 1H, J=5.4 Hz), 0.93 (t, 3H, J=7.1 Hz)

Example 6

3-(4-(12-hydroxydodecyl)phenyl)-1-isopropylquinolin-2(1H)-one wasdissolved in dry THF and Et₃N (4.0 equiv.) were added. The solution wasthen cooled to 0° C. with an ice-bath. Acryloyl chloride (1.1 equiv.)was added dropwise to the stirred solution. Directly after addition ofthe acryloyl chloride a colourless solid is precipitating. The reactionwas stirred overnight at room temperature. The suspension was filtratedand the solid was washed with additional THF. The filtrate wasevaporated under reduced pressure and purified by chromatography usingcyclohexane/EE as an eluent. The final monomer could be isolated in 74%yield.

The procedure with methacryloyl chloride is the same, as the abovedescribed.

The synthesis of the 6-hydroxy-1-methyl-3-phenylquinolin-2(1H)-onederivatives could be performed analogously to the above describedprocedure using the corresponding unsubstituted cinnamic acid derivativeand the para-methoxy substituted aniline derivative.

Selected NMR Data

¹H NMR (500 MHz, DMSO-d₆) δ 8.04 (s, 1H), 7.78 (d, 1H, J=8.0 Hz), 7.69(d, 2H, J=8.9 Hz), 7.61 (t, 1H, J=8.2 Hz), 7.53 (d, 1H, J=8.4 Hz), 7.28(t, 1H, J=7.4 Hz), 6.98 (d, 2H, J=8.9 Hz), 6.30 (d, 1H, J=17.1 Hz), 6.16(dd, 1H, J₁=17.3 Hz, J₂=10.3 Hz), 5.92 (d, 1H, J=10.3 Hz), 4.09 (t, 2H,J=6.6 Hz), 4.01 (t, 2H, J=6.7 Hz), 3.70 (s, 3H), 1.76-1.70 (m, 2H),1.62-1.57 (m, 2H), 1.45-1.40 (m, 2H), 1.37-1.22 (m, 16H)

m. p.: 60-61° C.

¹H NMR (500 MHz, CDCl₃) δ 7.95 (s, 1H), 7.84 (d, 1H, J=8.3 Hz), 7.73 (d,1H, J=8.0 Hz), 7.60-7.57 (m, 3H), 7.36 (t, 1H, J=7.5 Hz), 6.97 (d, 2H,J=8.8 Hz), 6.40 (dd, 1H, J₁=17.3 Hz, J₁=1.4 Hz), 6.12 (dd, 1H, J₁=17.3Hz, J₁=10.4 Hz), 5.81 (dd, 1H, J₁=10.4 Hz, J₁=1.4 Hz), 4.51 (t, 2H,J=6.7 Hz), 4.15 (t, 2H, J=6.8 Hz), 4.02 (t, 2H, J=6.6 Hz), 1.85-1.79 (m,4H), 1.70-1.64 (m, 2H), 1.51-1.45 (m, 3H), 1.40-1.30 (m, 17H), 0.93 (t,3H, J=7.2 Hz)

m.p.: 45-48° C.

¹H NMR (500 MHz, CDCl₃) δ 7.95 (s, 1H), 7.84 (d, 1H, J=8.4 Hz), 7.73 (d,1H, J=8.0 Hz), 7.60-7.57 (m, 3H), 7.37 (t, 1H, J=7.5 Hz), 6.97 (d, 2H,J=8.8 Hz), 6.10 (s, 1H), 5.54 (d, 1H, J=1.3 Hz), 4.52 (t, 2H, J=6.7 Hz),4.14 (t, 2H, J=6.7 Hz), 4.02 (t, 2H, J=6.5 Hz), 1.95 (s, 3H), 1.85-1.79(m, 4H), 1.69-1.65 (m, 2H), 1.50-1.30 (m, 23H), 0.93 (t, 3H, J=7.1 Hz)

Example 7 General Procedure for the Solvent Polymerization of theMonomers

The corresponding monomer was dissolved in dry N,N-dimethylformamid(65.0 equiv.) in a Schlenck-tube with a stirring bar. The solution wasdegassed performing three times freeze-evacuate-thaw cycles. After that,azoisobutyronitrile (AIBN, 0.05 equiv.) was added in one portion to thedegassed solution, which was heated up to 65° C. in an oil bath for aminimum of three days. The solution was cooled to room temperature andwas then poured dropwise into cold methanol (100 ml methanol/100 mgmonomer) while stirring. The precipitated polymer was collected on afrit or the solution was centrifuged several times to obtain the finalpolymer material.

Thus, polymers (P-1) to (P-47) can be synthesized from the respectivemonomers (M-1) to (M-47).

The invention claimed is:
 1. A compound of formula (I)

wherein a is 0 or 1; a′ is 0 or 1; R′, R² and R³ are H; one of R⁴ and R⁵is a group of formula (II)

and the other of R⁴ and R⁵ is H; R⁶ is a carbyl group for a′=1 and fora′=0 is H, F, Cl, Br, I, alkyl having from 1 to 20 carbon atoms,partially or completely halogenated alkyl having from 1 to 20 carbonatoms, aryl or heteroaryl; Sp is alkanediyl, alkenediyl or alkyndiylhaving at least 5 carbon atoms, where the alkanediyl, alkenediyl oralkyndiyl is unsubstituted or has at least one hydrogen atom replacedwith R¹⁶ where R¹⁶ is selected from the group consisting of alkyl havingfrom 1 to 10 carbon atoms, partially or completely halogenated alkylhaving from 1 to 10 carbon atoms, alkoxy having from 1 to 10 carbonatoms, and partially or completely halogenated alkoxy having from 1 to10 carbon atoms; X¹ is O; X² is O, S or N—R¹⁷; X³ is N—R¹⁷; R¹⁰, R¹¹,R¹³ and R¹⁴ are, at each occurrence independently of each other, H, F,Cl, Br, I, R¹⁵, R⁶-Sp-[X¹]_(a)-*, alkyl having from 1 to 20 carbonatoms, partially or completely halogenated alkyl having from 1 to 20carbon atoms, aryl or heteroaryl, provided that at least one of R¹⁰,R¹¹, R¹², R¹³ and R¹⁴ is R¹⁵; * each indicate the location of thelinkage of the group containing the * to the rest of the compound, R¹⁵is, at each occurrence independently, H, alkyl having from 1 to 20carbon atoms, partially or completely halogenated alkyl having from 1 to20 carbon atoms, alkoxy having from 1 to 20 carbon atoms, partially orcompletely halogenated alkoxy having from 1 to 20 carbon atoms,thioalkyl having from 1 to 20 carbon atoms or partially or completelyhalogenated thioalkyl having from 1 to 20 carbon atoms; and R¹⁷ is, ateach occurrence independently, alkyl having from 1 to 20 carbon atoms,provided that the compound of formula (I) comprises one groupR⁶-Sp-[X¹]_(a)-*.
 2. The compound according to claim 1, wherein saidcompound is of formula (I′)

wherein R⁶ is a carbyl group.
 3. The compound according to claim 1, saidcompound being of formula (I″)

wherein R⁶ is H, F, Cl, Br, I, alkyl having from 1 to 20 carbon atoms,partially or completely halogenated alkyl having from 1 to 20 carbonatoms, aryl or heteroaryl.
 4. The compound according to claim 1, whereinR⁴ is H and R⁵ is a group of formula (II).
 5. The compound according toclaim 2, wherein those of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ that are not R¹⁵are each H.
 6. The compound according to claim 1, wherein Sp is analkanediyl or an alkylidene group of at least 5 carbon atoms.
 7. Thecompound according to claim 1, wherein X² is O or S.
 8. An oligomer orpolymer of the compound according to claim 1, wherein the oligomer orpolymer is of the formula (I) of claim 1, wherein R⁶ is a group offormula (IV-B)

wherein X⁴ is O, S, C(═O), C(═O)O or N—R¹⁷; c is 0 or 1; R²⁰, R²¹ andR²² are, at each occurrence independently of each other, H, F, alkylhaving from 1 to 20 carbon atoms, partially or completely halogenatedalkyl having from 1 to 20 carbon atoms, aryl or heteroaryl; and the *adjacent to the [X⁴]_(c) indicates the location of the linkage of thegroup containing the * to the remainder of the following partialstructure of formula (I)

and the other two * each indicate a linkage to an adjacent repeatingunit of the oligomer or polymer.
 9. The oligomer or polymer according toclaim 8, wherein said oligomer or polymer comprises at least one unit M¹selected from formulae (I-B′), (I-B″-1), or (I-B″-2):

wherein one of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ is a group of formulaR⁶-Sp-[X¹]_(a)-* and R⁶ is a group of formula (IV-B);

wherein one of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ is a group of formulaR⁶-Sp-[X¹]_(a)-* and R⁶ is a group of formula (IV-B); said at least oneunit M¹ being, if there are two or more, at each occurrence the same ordifferent, wherein X⁴ is, at each occurrence independently, O, S orN—R¹⁷; c is at each occurrence 0 or 1; and R²⁰, R²¹ and R²² are, at eachoccurrence independently of each other, H, F, alkyl having from 1 to 20carbon atoms, partially or completely halogenated alkyl having from 1 to20 carbon atoms, aryl or heteroaryl.
 10. The oligomer or polymeraccording to claim 9, wherein said compound further comprises at leastone unit M², which at each occurrence is independently ethylene,propylene, an acrylate, a methacrylate or styrene.
 11. The oligomer orpolymer according to claim 10, said compound comprises units M¹ and M²in a ratio m₁:m₂ of from 0.01 to
 100. 12. The compound according toclaim 1, wherein R⁶ comprises an olefinically unsaturated group.
 13. Thecompound according to claim 1, wherein R⁶ is a group of formula (IV-A)

wherein c is 0 or 1; X⁴ is O, S, C(═O), C(═O)O or N—R¹⁷; and R²⁰, R²¹and R²² are each carbyl.
 14. The compound according to claim 1, whereinsaid compound is of formulae (I-A′), (I-A″-1), or (I-A″-2):

wherein one of R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ is a group of formulaR⁶—Sp-[X¹]_(a)-* and R⁶ is a group of formula (IV-A);

wherein one of R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ is a group of formulaR⁶—Sp-[X¹]_(a)-* and R⁶ is a group of formula (IV-A); wherein X⁴ is O, Sor N—R¹⁷; c is 0 or 1; and R²⁰, R²¹ and R²² are, at each occurrenceindependently of each other, H, F, alkyl having from 1 to 20 carbonatoms, partially or completely halogenated alkyl having from 1 to 20carbon atoms, aryl or heteroaryl.
 15. A composition comprising acompound of claim
 1. 16. An intraocular lens article comprising thecomposition of claim
 15. 17. The intraocular lens article according toclaim 16, wherein said article is an optically active article.
 18. Theintraocular lens article according to claim 16, wherein said article isan ophthalmic device.
 19. The process of forming an intraocular lensarticle, said process comprising a) providing a composition comprisingthe compound of claim 1; and b) subsequently forming the intraocularlens article of said composition.
 20. The process of changing theoptical properties of an intraocular lens article of claim 16, saidprocess comprising a) providing an intraocular lens article of claim 16,and b) subsequently exposing said article to irradiation having awavelength of at least 200 nm and at most 1500 nm.
 21. The compoundaccording to claim 1, wherein said compound is a compound according toformulae (M-1) to (M-47):


22. The composition according to claim 15, wherein said compositionfurther comprises a UV absorber, an antioxidant, and/or a crosslinker.23. The intraocular lens article according to claim 18, wherein saidophthalmic device is a lens, a keratoprostheses, a cornea inlay, orcornea ring.
 24. An optically active intraocular lens article, whichcomprises an oligomer or polymer according to claim
 8. 25. An opticallyactive intraocular lens article, which comprises an oligomer or polymeraccording to claim
 9. 26. An optically active intraocular lens article,which comprises an oligomer or polymer according to claim
 10. 27. Anoptically active intraocular lens article which comprises, a copolymercomprising: one or more units derived by polymerization of a compound offollowing formula (I); and one or more different polymer units:

wherein a is 0 or 1; a′ is 0 or 1; R′, R² and R³ are H; one of R⁴ and R⁵is a group of formula (II)

and the other of R⁴ and R⁵ is H; each indicate the location of thelinkage of the group containing the * to the rest of the compound, R⁶ isa carbyl group for a′=1 and for a′=0 is selected from the groupconsisting of H, F, Cl, Br, I, alkyl having from 1 to 20 carbon atoms,partially or completely halogenated alkyl having from 1 to 20 carbonatoms, aryl and heteroaryl; Sp is selected from the group consisting ofalkanediyl, alkenediyl and alkyndiyl having at least 5 carbon atoms,where the alkanediyl, alkenediyl or alkyndiyl is unsubstituted or has atleast one hydrogen atom replaced with R¹⁶ where R¹⁶ is selected from thegroup consisting of alkyl having from 1 to 10 carbon atoms, partially orcompletely halogenated alkyl having from 1 to 10 carbon atoms, alkoxyhaving from 1 to 10 carbon atoms, and partially or completelyhalogenated alkoxy having from 1 to 10 carbon atoms; X¹ is O X² is O, Sor; X³ is N—R¹⁷; R′°, R¹¹R¹², R¹³ and R¹⁴ are at each occurrenceindependently of each other selected from the group consisting of H, F,Cl, Br, I, R¹⁵, R⁶—Sp-[X¹]_(a)-*, alkyl having from 1 to 20 carbonatoms, partially or completely halogenated alkyl having from 1 to 20carbon atoms, aryl and heteroaryl, where R⁶ is a carbyl group or H, F,Cl, Br or I, and provided that at least one of R¹⁰, R¹¹, R¹², R¹³ andR¹⁴ is R¹⁵; R¹⁵ is at each occurrence independently selected from thegroup consisting of alkyl having from 1 to 20 carbon atoms, partially orcompletely halogenated alkyl having from 1 to 20 carbon atoms, alkoxyhaving from 1 to 20 carbon atoms, partially or completely halogenatedalkoxy having from 1 to 20 carbon atoms, thioalkyl having from 1 to 20carbon atoms, and partially or completely halogenated thioalkyl havingfrom 1 to 20 carbon atoms; and R¹⁷ is at each occurrence independentlyselected from alkyl having from 1 to 20 carbon atoms, provided that thecompound of formula (I) comprises one group R⁶—Sp-[X¹]_(a)-* where R⁶ isa polymerizable carbyl group.